Alumina carrier, method for preparing the same, and use thereof

Abstract

This invention discloses an alumina support, its preparation method, and its application. The method includes the following steps: mixing hydrated alumina with isobutylene-maleic anhydride copolymer, then adding ammonia and deionized water, kneading, molding, drying, and calcining to obtain the alumina support. The isobutylene-maleic anhydride copolymer simultaneously acts as a binder, dispersant, and pore expander. The alumina support preparation method provided by this invention is simple, environmentally friendly, and low-cost. The resulting alumina support has large pore size and volume, high mechanical strength, and low impurity residue, thereby improving catalyst efficiency. The obtained alumina support can be used as an active protectant and demetallization catalyst support in residual oil hydrotreating.

Description

Technical Field

[0001] This invention relates to the field of alumina support preparation, and particularly to an alumina support, its preparation method, and its application. Background Technology

[0002] Currently, with the increasing heavy and degraded quality of global petroleum resources, there is an urgent need to develop clean and efficient heavy oil processing technologies. Hydrogenation is the most effective technology for processing heavy and residual oil feedstocks. Through hydrogenation, most metallic impurities and sulfur are removed, while the carbon residue value is reduced, improving the quality of heavy oil and making further efficient and clean processing possible. The combination of heavy and residual oil hydrotreating with heavy oil catalytic cracking can not only maximize the conversion of low-value and environmentally polluting residual oil and significantly increase the yield of light oil, but also obtain high-value-added, high-quality clean oil products. This technology combination has become a core technology for refining enterprises processing sulfur-containing crude oil to improve economic efficiency.

[0003] Metals such as Na, Ca, Ni, and V deposited on hydrotreating catalysts in heavy oil can cause permanent poisoning, a crucial factor to consider in the heavy oil hydrotreating process. Active protective agents and hydrodemetallizing catalysts are key technologies in heavy oil hydrotreating, primarily responsible for removing most of the Ni and V metal impurities from the feedstock, protecting downstream desulfurization (HDS) and denitrification (HDN) catalysts, and possessing a certain desulfurization capacity. Both types of catalysts require not only excellent metal removal capabilities but also high metal impurity tolerance. Since most metal impurities in residual oil reside in gums and asphaltenes, which are the largest, most structurally complex, and most polar components in petroleum, they exhibit significant diffusion resistance. Demetallizing agents are constrained by the mass transfer and diffusion efficiency of the carrier, easily leading to pore blockage, severely uneven distribution of removed impurities, and limited metal tolerance. All of these factors result in significant waste of internal catalyst space, preventing the maximization of individual catalyst efficiency. Therefore, both types of catalysts must possess large pore volume, pore size, and good pore permeability to facilitate the diffusion, reaction, and deposition of macromolecular substances such as asphaltenes containing metallic impurities in residual oil feedstock. One solution is to use macroporous alumina supports. During the reaction, the large pores with a diameter of over 100 nm provide channels for the diffusion of macromolecular reactants, promoting the diffusion and deposition of impurities into the internal pores of the catalyst, thereby giving the catalyst high demetallization activity and high impurity tolerance.

[0004] To obtain alumina carrier materials with macroporous structures, researchers have employed methods such as pore expanders and hydrothermal treatment to achieve this structure. There is a considerable body of literature on the synthesis of macroporous alumina materials using pore expanders, which can be categorized into two types based on the type of pore expander: hard pore expanders and soft pore expanders.

[0005] Hard pore-expanding agent methods, represented by activated carbon, can yield relatively good macroporous alumina. US19820384626 discloses a method using carbon black as a pore-expanding agent to obtain macroporous alumina with a pore size distribution of 15–300 nm. However, due to the uneven particle diameter distribution of carbon black, it is difficult to prepare macroporous alumina with a concentrated pore size distribution. CN201410347665.X discloses a method for preparing macroporous, high-strength alumina by adding pore-expanding agents such as polyacrylamide, polyvinyl alcohol, alkyl cellulose, guar gum powder, and starch to obtain a macroporous alumina support. The amount of pore-expanding agent used accounts for 10%–30% of the alumina, but the specific pore size range is not disclosed. Although hard pore-expanding agent methods can yield relatively good macroporous alumina supports, the amount of pore-expanding agent used is preferably greater than 20%, which leads to a significant increase in processing costs. Furthermore, the decomposition of a large amount of pore-expanding agent does not meet the requirements of low-carbon and environmentally friendly development.

[0006] CN201010509425.7 discloses a method for co-expanding pores using hydrothermal heating and a pore-expanding agent to prepare an alumina carrier with a macroporous structure. Through hydrothermal assisted pore-expanding, the amount of pore-expanding agent can be reduced to 3% to 10%, but the auxiliary hydrothermal heating results in increased energy consumption.

[0007] CN200310103035.X discloses a method for preparing macroporous alumina, using polyvinyl alcohol, polypropylene alcohol, and polyethylene glycol as soft pore expanders. By adding 1% polyethylene glycol, the pore volume with a diameter greater than 100 nm accounts for 26.2% of the total pore volume. Soft pore expanders have the advantages of low dosage and good pore-expanding effect; however, the poor solubility of high molecular weight alcohol-based soft pore expanders in water limits their use in expanding ultra-large porosity alumina.

[0008] CN201410148773.4 discloses a method for preparing porous alumina microspheres, comprising the following steps: 1) dissolving a surfactant in deionized water and stirring to form an aqueous phase; 2) mixing a chelating agent, an alumina precursor, and n-octanol and stirring to form an oil phase; 3) adding Span80 and a pore-forming agent to the oil phase and stirring; 4) pouring the clarified oil phase obtained in step 3) into the aqueous phase and continuously stirring to emulsify; 5) vacuum filtering the product obtained in step 4), washing and drying the resulting filter cake to obtain porous alumina microspheres. These microspheres have an internally closed macroporous structure, with a size of 1–100 μm. This invention utilizes a sol-gel process between a pore-forming agent and an emulsion to obtain porous metal microspheres with an internally closed macroporous structure. The porous microspheres are prepared using the principle of phase separation. The internal closed pore size is 50 nm–5 μm. The pore-forming agent is polyvinylpyrrolidone, polyacrylamide, or polyacrylic acid. This invention uses a large number of surfactants, chelating agents, and pore-forming agents, and involves many raw materials and a complex synthesis process.

[0009] CN201310499233.6 discloses a method for preparing an alumina support, comprising the following steps: first, a neutralization reaction is carried out between an alkaline precipitant aqueous solution and an acidic aluminum salt aqueous solution to obtain a precipitate slurry; then, a water-soluble resin is added to the precipitate slurry and aged using microwave heating; finally, the aged mixture is filtered, washed, dried, and shaped to obtain the final alumina support. The alumina support prepared by this method has a high proportion of pores with a diameter of 10–20 nm, reaching 60%–80% of the total pore volume, while the proportion of macropores is relatively small.

[0010] CN201110116418.5 discloses a mesoporous spherical alumina and a method for preparing the mesoporous spherical alumina using a pore-expanding agent. The method employs an oil column molding process, adding a pore-expanding agent with a guiding function to the alumina sol during preparation. During the molding and aging process of the alumina sol, the presence of the pore-expanding agent creates a large number of mesoporous structures within the alumina spheres. The pore-expanding agent is an organic monomer or a linear polymer. The organic monomer is one of acrylic acid, ammonium acrylate, acrylamide, and allyl alcohol, and the linear polymer is one of polyvinyl alcohol, polyacrylamide, and polyacrylamide. The specific surface area of ​​the resulting mesoporous spherical alumina is 150–300 μm. 2 / g, particle diameter 0.1–5mm, pore volume 0.7–1.5ml / g, pores with a diameter of 2–40nm greater than 97%, bulk density 0.30–0.80g / cm³ 3 The crushing strength is 70–250 N / particle. The mesoporous spherical alumina prepared by this invention using a pore-expanding agent has a relatively concentrated pore diameter, and the proportion of macropores >100 nm is very small overall, making it unsuitable as a support for heavy oil or residue oil hydrogenation catalysts.

[0011] CN110394197A discloses an ordered hierarchical porous alumina support, its preparation method, and its application. The preparation method includes the following steps: first, a soft template agent, a soluble aluminum salt, a binder, and a precipitant are mixed together to form a supersol-polymerized micelle; then, a hard template agent is mixed with the supersol-polymerized micelles for in-situ synthesis to obtain secondary nano-self-assembled aluminum hydroxide; finally, the secondary nano-self-assembled aluminum hydroxide is washed with water and dried, followed by calcination to obtain the ordered hierarchical porous alumina support. This method is exceptionally complex and requires excessively large dosages, leading to high costs, high energy consumption during calcination, and high carbon emissions. Furthermore, the hard template agent used in this method introduces other elemental impurities into the alumina support, severely affecting its physical properties.

[0012] In summary, the existing macroporous alumina carrier preparation technology has the following problems: (1) When alumina is formed, acidic substances such as nitric acid and acetic acid are often added as adhesives, resulting in small pore volume and pore size of the alumina carrier; (2) A large amount of organic / inorganic pore expanders are added, which generates a large amount of greenhouse gases and harmful gases during the calcination process, resulting in high environmental pressure. This not only increases the carrier preparation cost, but also has a negative impact on the strength of the carrier, and also results in high residual impurities in the carrier; (3) Extrusion aids such as starch and guar gum are required, which increases the carrier preparation cost. Summary of the Invention

[0013] To address the shortcomings of existing technologies, the purpose of this invention is to provide a method different from conventional methods such as hydrothermal methods, the addition of physical or chemical pore expanders. Instead, it employs a mixture of a small amount of isobutylene-maleic anhydride copolymer and hydrated alumina. The isobutylene-maleic anhydride copolymer's unique structure, with its numerous ordered carboxyl groups, encapsulates the alumina, creating electrostatic repulsion between the encapsulated alumina molecules and increasing the intermolecular porosity, thereby expanding the pore size of the alumina support. Secondly, the isobutylene-maleic anhydride copolymer itself acts as a binder and dispersant, resulting in an alumina support with both large pore size and volume, and high mechanical strength, thus improving catalyst efficiency. Thirdly, the isobutylene-maleic anhydride copolymer has extremely low ash content after calcination, leaving almost no residue during the alumina support preparation process and not affecting the properties of the support or catalyst.

[0014] Therefore, the present invention provides a method for preparing an alumina carrier, comprising the following steps: mixing hydrated alumina, isobutylene-maleic anhydride copolymer, ammonia, and deionized water, kneading, molding, drying, and calcining to obtain the alumina carrier.

[0015] Specifically, isobutylene-maleic anhydride copolymer can simultaneously act as an adhesive, dispersant, and pore expander.

[0016] Specifically, the mixing method for hydrated alumina, isobutylene-maleic anhydride copolymer, ammonia, and deionized water can be either sequential mixing or mixing isobutylene-maleic anhydride copolymer with ammonia to form a clear solution, which is then mixed with hydrated alumina and deionized water.

[0017] In the method for preparing the alumina carrier of the present invention, preferably, the isobutylene-maleic anhydride copolymer is selected from at least one of the standard type, amide-ammonium salt type, imide type, and crosslinking type.

[0018] The method for preparing the alumina carrier described in this invention does not particularly limit the properties of the isobutylene-maleic anhydride copolymer, but preferably, the molecular weight distribution of the isobutylene-maleic anhydride copolymer is in the range of 6,000-400,000.

[0019] The method for preparing the alumina carrier described in this invention does not particularly limit the type of hydrated alumina. Preferably, the hydrated alumina is selected from at least one of gibbsite, boehmite, pseudoboehmite, and amorphous aluminum hydroxide; more preferably, pseudoboehmite is used.

[0020] The method for preparing the alumina support of the present invention does not particularly limit the amount of isobutylene-maleic anhydride copolymer added. The amount added can be adjusted according to the pore size requirements of the prepared alumina support. Preferably, the amount of isobutylene-maleic anhydride copolymer added is 0.1%-10.0% of the weight of the hydrated alumina, more preferably 0.1%-5.0%, and most preferably 0.1%-2.0%.

[0021] The method for preparing the alumina carrier according to the present invention does not particularly limit the amount of ammonia added. Preferably, the amount of ammonia added is 20-100% of the weight of the isobutylene-maleic anhydride copolymer, and the concentration of the ammonia is 20-40w.

[0022] The method for preparing the alumina carrier described in this invention does not particularly limit the calcination conditions, but preferably, the calcination temperature is 500-1100°C and the time is 0.5-4 hours.

[0023] The method for preparing the alumina carrier described in this invention does not particularly limit the drying conditions, but preferably, the drying temperature is 100-120°C and the time is 0.5-6 hours.

[0024] Therefore, the present invention also provides an alumina carrier, which is prepared by the above-described preparation method, has a pore volume of 1.0-2.5 ml / g, an average pore size of 30-100 nm, a pore volume with a pore size >100 nm accounting for 30-70% of the total pore volume, a carrier strength >15 N / mm, and impurity residue <0.1%.

[0025] Therefore, the present invention also provides an application of an alumina support in the application of the alumina support as an active protective agent or demetallization catalyst in the hydrotreating of residual oil.

[0026] In summary, the preparation method provided by this invention has the advantages of simple preparation process, environmentally friendly preparation process, and low cost. The preparation method of this invention utilizes the unique structure of the isobutylene-maleic anhydride copolymer itself, which has a large number of ordered carboxyl groups to encapsulate alumina, and the encapsulated alumina molecules provide electrostatic repulsion to each other, increasing the intermolecular porosity of alumina and thus achieving the purpose of expanding the pore size of the alumina support. The relatively low amount of isobutylene-maleic anhydride copolymer used in the preparation method of this invention can also achieve a good effect of expanding the pore size of the alumina support. Furthermore, the isobutylene-maleic anhydride copolymer itself can also act as a binder and dispersant. The alumina support obtained by this method has the advantages of large pore size and pore volume, high mechanical strength, low impurity residue, and increased pore volume ratio of alumina support with pore size >100nm. Moreover, the alumina support prepared by the method of this invention can be used as an active protective agent and demetallization catalyst support for residue oil hydrotreating. Detailed Implementation

[0027] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions, and percentages not specified are by weight.

[0028] The present invention provides a method for preparing an alumina carrier, comprising the following steps: mixing hydrated alumina with isobutylene-maleic anhydride copolymer, adding ammonia and deionized water, kneading, molding, drying and calcining to obtain the alumina carrier.

[0029] Specifically, isobutylene-maleic anhydride copolymer can simultaneously act as an adhesive, dispersant, and pore expander.

[0030] In the method for preparing the alumina carrier of the present invention, preferably, the isobutylene-maleic anhydride copolymer is selected from at least one of the standard type, amide-ammonium salt type, imide type, and crosslinking type.

[0031] The method for preparing the alumina carrier described in this invention does not particularly limit the properties of the isobutylene-maleic anhydride copolymer, but preferably, the molecular weight distribution of the isobutylene-maleic anhydride copolymer is in the range of 6,000-400,000.

[0032] The method for preparing the alumina carrier described in this invention does not particularly limit the type of hydrated alumina. Preferably, the hydrated alumina is selected from at least one of gibbsite, boehmite, pseudoboehmite, and amorphous aluminum hydroxide; more preferably, pseudoboehmite. The hydrated alumina can be a commercially available product or prepared by any method in the prior art, such as pseudoboehmite prepared by the aluminum sulfate-sodium aluminate method.

[0033] The method for preparing the alumina support of the present invention does not particularly limit the amount of isobutylene-maleic anhydride copolymer added. The amount added can be adjusted according to the pore size requirements of the prepared alumina support. Preferably, the amount of isobutylene-maleic anhydride copolymer added is 0.1%-10.0% of the weight of the hydrated alumina, more preferably 0.1%-5.0%, and most preferably 0.1%-2.0%.

[0034] The method for preparing the alumina carrier described in this invention does not particularly limit the amount of ammonia added, but preferably, the amount of ammonia added is 20 to 100% of the weight of the isobutylene-maleic anhydride copolymer.

[0035] The method for preparing the alumina carrier described in this invention does not particularly limit the calcination conditions, but preferably, the calcination temperature is 500-1100°C and the time is 0.5-4 hours.

[0036] The method for preparing the alumina carrier described in this invention does not particularly limit the drying conditions, but preferably, the drying temperature is 100-120°C and the time is 0.5-6 hours.

[0037] Therefore, the present invention also provides an alumina carrier, which is prepared by the above-described preparation method, has a pore volume of 1.0-2.5 ml / g, an average pore size of 30-100 nm, a pore volume with a pore size >100 nm accounting for 30-70% of the total pore volume, a carrier strength >15 N / mm, and impurity residue <0.1%.

[0038] Therefore, the present invention also provides an application of an alumina support in the application of an active protective agent or demetallization catalyst in the hydrotreating of residual oil.

[0039] In the following examples and comparative examples, the isobutylene-maleic anhydride copolymers used include standard type, amide-ammonium salt type, imide type, crosslinked type, etc., all under the unified trade name ISOBAM-XXX, with the specific type indicated by the trade name. The pore structure of the alumina support was determined using mercury porosimetry.

[0040] Example 1

[0041] Weigh 564g of macroporous pseudoboehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shandong Binzhou Juchuang Company, and 8g of ISOBAM-600 (standard type, molecular weight distribution 7000) powder, mix them evenly, then add 32g of 25w% ammonia water and 750g of deionized water, knead into a plastic body, and then extrude it into a four-leaf clover-shaped carrier wet strip with a diameter of 1.4mm on an extruder. Dry the wet strip at 120℃ for 3.0 hours, and then place it in a high-temperature calcination furnace and keep it at 950℃ for 3 hours to obtain carrier A. Its physicochemical properties are listed in Table 1.

[0042] Example 2

[0043] Weigh 4g of ISOBAM-110 (amide-ammonium salt type, molecular weight distribution 400,000) powder and slowly add it to 16g of 25w% ammonia water, stirring thoroughly until the solution is clear and free of visible particles. Weigh 564g of macroporous boehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shandong Binzhou Juchuang Company and 660g of deionized water. Mix the boehmite, deionized water, and the above clear solution, knead into a plastic body, and then extrude it into a clover-shaped carrier wet strip with a diameter of 1.4mm on an extruder. Dry the wet strip at 120℃ for 3.0 hours, and then place it in a high-temperature calcination furnace and keep it at 950℃ for 3 hours to obtain carrier B. Its physicochemical properties are listed in Table 1.

[0044] Example 3

[0045] 564g of macroporous pseudoboehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shanxi Juhua New Materials Co., Ltd., and 8g of ISOBAM-06 (standard type, molecular weight distribution 200,000) powder were weighed and mixed evenly. Then, 8g of 25w% ammonia water and 800g of deionized water were added and kneaded into a plastic body. The mixture was then extruded into clover-shaped wet strips with a diameter of 1.4mm on an extruder. The wet strips were dried at 110℃ for 4.0 hours and then placed in a high-temperature calcination furnace and kept at 900℃ for 4 hours to obtain carrier C. Its physicochemical properties are listed in Table 1.

[0046] Example 4

[0047] Weigh 20g of ISOBAM-Kl-gel (crosslinked type, molecular weight distribution 350,000) powder and slowly add it to 12.5g of 40w% ammonia water, stirring thoroughly until the solution is clear and free of visible particles. Weigh 560g of macroporous boehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shanxi Juhua New Materials Co., Ltd., and 531g of deionized water. Mix the boehmite, deionized water, and the above clear solution, knead into a plastic body, and then extrude it into a clover-shaped carrier wet strip with a diameter of 1.4mm on an extruder. Dry the wet strip at 100℃ for 6.0 hours, and then place it in a high-temperature calcination furnace and keep it at 600℃ for 3 hours to obtain carrier D. Its physicochemical properties are listed in Table 1.

[0048] Example 5

[0049] Weigh 2g of ISOBAM-304 (imide type, molecular weight distribution 180,000) powder and 2g of ISOBAM-18 (standard type, molecular weight distribution 100,000) powder, and slowly add them together to 4g of 20w% ammonia water. Stir thoroughly until the solution is clear and free of visible particles. Weigh 560g of macroporous boehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shanxi Juhua New Materials Co., Ltd., and 760g of deionized water. Mix the boehmite, deionized water, and the above clear solution, knead into a plastic body, and then extrude it into a four-leaf clover-shaped carrier wet strip with a diameter of 1.4mm on an extruder. Dry the wet strip at 120℃ for 2.0 hours, and then place it in a high-temperature calcination furnace and keep it at 970℃ for 3 hours to obtain carrier E. Its physicochemical properties are listed in Table 1.

[0050] Example 6

[0051] 564g of macroporous pseudoboehmite dry adhesive powder (dry basis content 71.0wt%) produced by Shanxi Juhua New Materials Co., Ltd., and 40g of ISOBAM-06 (standard type, molecular weight distribution 200,000) powder were weighed and mixed evenly. Then, 40g of 25w% ammonia water and 650g of deionized water were added and kneaded into a plastic body. The mixture was then extruded into clover-shaped carrier wet strips with a diameter of 1.4mm on an extruder. The wet strips were dried at 110℃ for 4.0 hours and then placed in a high-temperature calcination furnace and kept at 900℃ for 4 hours to obtain carrier F. Its physicochemical properties are listed in Table 1.

[0052] Comparative Examples 1-4: Alumina supports prepared using existing techniques.

[0053] Comparative Example 1

[0054] The difference from Example 1 is that polyacrylamide disclosed in CN201410347665.X was added as a pore expander, and the rest is the same as in Example 1, to obtain carrier G, whose physicochemical properties are listed in Table 1.

[0055] Comparative Example 2

[0056] The difference from Example 1 is that carbon black powder disclosed in CN201010509425.7 was added as a pore expander. Otherwise, it is the same as Example 1, and the carrier H is obtained. Its physicochemical properties are listed in Table 1.

[0057] Comparative Example 3

[0058] The difference from Example 1 is that the water-soluble resin disclosed in CN201310499233.6 is added as a pore expander, and the rest is the same as in Example 1, to obtain carrier I, whose physicochemical properties are listed in Table 1.

[0059] Comparative Example 4

[0060] The difference from Example 1 is the addition of polyisobutylene triethanolamine maleate disclosed in CN1296136C as an organic pore expander. Otherwise, it is the same as Example 1, and the resulting carrier J is shown in Table 1.

[0061] Table 1 Physical and chemical properties of the carrier

[0062]

[0063] The results in Table 1 show that the proportion of pores >100 nm in the supports prepared by the comparative method is too small, and the amount of residual impurities is too large. Supports G and J have no pore size distribution >100 nm at all, and the pore-expanding agent has no pore-expanding effect. Compared with the comparative examples, the alumina supports prepared by the present invention have advantages such as large pore volume, large average pore size, high lateral pressure strength, less residual impurities, and an increased proportion of pores >100 nm in the alumina supports. Therefore, the alumina supports prepared by the method of the present invention can better provide channels for the diffusion of macromolecular reactants, promoting the diffusion and deposition of impurities into the internal pores of the catalyst. Furthermore, compared with the comparative examples, the amount of isobutylene-maleic anhydride copolymer pore-expanding agent added is reduced, and the total mass of additives as a percentage of the alumina mass is significantly lower, effectively reducing the support preparation cost, simplifying the preparation process, and greatly reducing the emission of greenhouse gases and harmful gases during the preparation process.

[0064] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the present invention.

Claims

1. A process for the preparation of an alumina support, characterized in that, The method comprises the following steps: mixing hydrated alumina, isobutylene-maleic anhydride copolymer, ammonia water and deionized water, then kneading, shaping, drying and calcining to obtain the alumina carrier. The isobutylene-maleic anhydride copolymer is selected from at least one of standard type, amide-ammonium salt type, imide type and crosslinked type. The molecular weight distribution of the isobutylene-maleic anhydride copolymer is in the range of 6000-400000. The isobutylene-maleic anhydride copolymer is added in an amount of 0.1%-10.0% by weight of the hydrated alumina.

2. The production method according to claim 1, characterized by, The hydrated alumina is selected from at least one of gibbsite, boehmite, pseudoboehmite and amorphous aluminum hydroxide.

3. The production method according to claim 2, characterized by, The hydrated alumina is pseudoboehmite.

4. The method of claim 1, wherein, The isobutylene-maleic anhydride copolymer is added in an amount of 0.1%-2.0% by weight of the hydrated alumina.

5. The preparation method according to claim 1, characterized in that, The ammonia water is added in an amount of 20-100% by weight of the isobutylene-maleic anhydride copolymer, and the concentration of the ammonia water is 20-40w%.

6. The method of claim 1, wherein, The calcination temperature is 500-1100℃, and the time is 0.5-4 hours; the drying temperature is 100-120℃, and the time is 0.5-6 hours.

7. An alumina support produced by the method of any one of claims 1 to 6, characterized in that, The pore volume is 1.0-2.5ml / g, the average pore size is 30-100nm, the pore volume of the pores with a pore size of >100nm accounts for 30-70% of the total pore volume, the carrier strength is >15N / mm, and the impurity residue is <0.1%.

8. Use of an alumina support, characterized in that The alumina carrier prepared by the preparation method of any one of claims 1-6 is applied in a residual oil hydroprocessing active protectant or a demetallization catalyst.

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